This invention is generally directed to toner compositions, and more specifically, the present invention relates to developer compositions with toner compositions comprised of liquid glass or multiblock resins. More specifically, in one embodiment of the present invention there are provided developer compositions formulated by, for example, admixing toner compositions containing multiblock polymeric toner resins and carrier components. In one embodiment of the present invention there are provided toner compositions with multiblock or liquid glass polymers, such as (A-B).sub.n wherein n represents the number of repeating polymer segments and where A and B represent monomeric or oligomeric segments, which components possess in an embodiment of the present invention a desirable low fusion and fusing energy; are easily jettable or processable into toner compositions; possess low interfacial surface energies between the polymer segments enabling low temperature fusing; are optically clear, and with the multisegment polymers illustrated herein there can in embodiments be fabricated brittle, rubbery, or other similar toner polymers with an optimized melt viscosity profile, that is for example added segments increase the molecular weight and can increase the melt viscosity of the resulting polymer without substantially adversely influencing the glass transition temperature; and lowering the fusing temperature characteristics of the toner resin. The polymers of the present invention are processable by conventional toner means, that is these materials are extrudable, melt mixable and jettable. The resulting toner materials in an embodiment of the present invention possess excellent triboelectric charging characteristics and also fuse and fix to paper to about 100.degree. F. lower than conventional toner polymers. Also, toner compositions formulated with the aforementioned multisegment polymers have similar advantages as illustrated herein. Thus, for example, the toner compositions in an embodiment of the present invention possess lower fusing temperatures, and therefore lower fusing energies are required for fixing, thus enabling less power consumption during fusing, and permitting extended lifetimes for the fuser systems selected. The toners of the present invention can be fused (fuser roll set temperature) at temperatures of between 220.degree. and 270.degree. F. in an embodiment of the present invention as compared to a number of currently commercially available toners which fuse at temperatures of from about 300.degree. to about 325.degree. F. With further respect to the present invention, the multiblock, or liquid glass polymers contain, for example, in embodiments thereof an oligomeric glassy segment with a glass transition temperature of from about 24.degree. to about 72.degree. C., a degree of polymerization of from about 1 to about 100, while the liquid phase has a degree of polymerization of from about 1 to about 100 or about one third of the molecular weight of the glassy content. When the liquid phase is polybutadiene, the butadiene may be incorporated as 1,4 olefinic cis, trans, or 1,2-vinyl enchainments, and the like. Isoprene behaves similarly. Preferred "nonblocking" properties, that is noncaking or retaining substantially all the properties of a free flowing powder, are obtained with, for example, compositions having a high level of the aforementioned 1,2-vinyl enchainments. In an embodiment the multiblock polymers of the present invention, wherein A can represent the glassy component and B can represent the liquid component, have a number average molecular weight of from about 3,000 to about 100,000 and preferably from about 6,000 to about 50,000. Also, the economical toner and developer compositions of the present invention are particularly useful in electrophotographic imaging and printing systems, including color, especially xerographic imaging processes that are designed for the generation of full color images.
The electrostatographic process, and particularly the xerographic process, is well known. This process involves the formation of an electrostatic latent image on a photoreceptor, followed by development, and subsequent transfer of the image to a suitable substrate. Numerous different types of xerographic imaging processes are known wherein, for example, insulative developer particles of conductive toner compositions are selected depending on the development systems used. Of known value with respect to the aforementioned developer compositions, for example, is the appropriate triboelectric charging values associated therewith as it is these values that can enable continued constant developed images of high quality and excellent resolution; and admixing characteristics. Specifically, thus toner and developer compositions are known, wherein there are selected as the toner resin styrene acrylates, styrene methacrylates, and certain styrene butadienes including those available as Pliolites. Other resins have also been selected for incorporation into toner compositions inclusive of the polyesters as illustrated in U.S. Pat. No. 3,590,000. Moreover, it is known that single component magnetic toners can be formulated with styrene butadiene resins, particularly those resins available as Pliolite. In addition, positively charged toner compositions containing various resins, inclusive of certain styrene butadienes and charge enhancing additives, are known. For example, there are described in U.S. Pat. No. 4,560,635, the disclosure of which is totally incorporated herein by reference, positively charged toner compositions with distearyl dimethyl ammonium methyl sulfate charge enhancing additives. The '635 patent also illustrates the utilization of suspension polymerized styrene butadienes for incorporation into lower compositions, reference for example working Example IX.
In a patentablility search report, the following United States patents were listed:
U.S. Pat. No. 3,965,021 Patentee: Clemens et al. Issued: Jun. 21, 1976 PA0 U.S. Pat. No. 3,853,778 Patentee: Buckley et al. Issued: Dec. 4, 1974 PA0 U.S. Pat. No. 3,967,962 Patentee: O'Malley Issued: Jul. 6, 1976 PA0 U.S. Pat. No. 4,528,257 Patentee: Polderman et al. Issued: Jul. 9, 1985 PA0 I. Polypentenes-(C.sub.5 H.sub.10).sub.x PA0 II. Polytetradecenes-(C.sub.14 H.sub.28).sub.x PA0 III. Polypentadecenes-(C.sub.15 H.sub.30).sub.x PA0 IV. Polyhexadecenes-(C.sub.16 H.sub.32).sub.x PA0 V. Polyheptadecenes-(C.sub.17 H.sub.34).sub.x PA0 VI. Polyoctadecenes-(C.sub.18 H.sub.36).sub.x PA0 VII. Polynonadecenes-(C.sub.19 H.sub.38).sub.x ; and PA0 VIII. Polyeicosenes-(C.sub.20 H.sub.40).sub.x.
and noted as background interest U.S. Pat. Nos. 2,940,934; 3,876,610; 3,974,078; 4,262,077; 4,272,600 and 4,385,107.
Clements discloses, for example, a toner resin comprised of a physical blend of incompatible polymers, and a toner in which the resinous material is comprised of at least two polymers, reference for example the Abstract of the Disclosure. The segments of the block copolymers may be polystyrene and polybutadiene. For example, as disclosed in column 3, the polyblends are either graft or block copolymers that have relatively long chains of each polymer component, and therefore each polymeric component retains its own identity. In column 3 of U.S. Pat. No. 3,965,021, there is disclosed a toner comprised of a resinous material of a polyblend of at least two types of polymers, which polyblend may either be a physical mixture, or a chemical mixture of either a block copolymer or a graft copolymer, see lines 28 and 29 of column 3, and note the disclosure in column 3, beginning at line 58; the glass transition information in columns 5 and 6; and the working Examples, including Examples 27 and 28.
Buckley, for example, discloses a toner resin comprised of a polymer selected from the group consisting of a crystalline homopolymer or copolymer having an amorphous backbone and side-chain crystallinity derived from polymerizable monomers having at least 14 carbon atoms, reference for example the Abstract of the Disclosure, note also columns 4, 5 and 6, and the working Examples.
O'Malley discloses, for example, a semicrystalline toner resin comprised of block or graft copolymers consisting of at least one crystalline or crystallizable polymeric segment chemically linked to at least one amorphous polymeric segment, see the Abstract of the Disclosure for example; note also column 4, beginning at line 54, and columns 6 and 7.
Polderman also discloses a semicrystalline toner resin comprised of immisicible crystalline and amorphous polymeric blocks, see for example the Abstract of the Disclosure.
Numerous patents are in existence that illustrate toner compositions with various types of toner resins including, for example, U.S. Pat. Nos. 4,104,066, polycarolactones; 3,547,822, polyesters; 4,049,447, polyesters; 4,007,293, polyvinyl pyridine-polyurethane; 3,967,962, polyhexamethylene sebaccate; 4,314,931, polymethyl methacrylates; Reissue 25,136, polystyrenes; and 4,469,770, styrene butadienes.
In U.S. Pat. No. 4,529,680, there are disclosed magnetic toners for pressure fixation containing methyl-1-pentene as the main component. More specifically, there are illustrated in this patent, reference column 2, beginning at line 66, magnetic toners with polymers containing essentially methyl-1-pentene as the main component, which polymer may be a homopolymer or copolymer with other alpha-olefin components. It is also indicated in column 3, beginning at around line 14, that the intrinsic viscosity of the polymer is of a specific range, and further that the melting point of the polymer is in a range of 150.degree. to 240.degree. C. and preferably 180.degree. to 230.degree. C. Other patents that may be of background interest include U.S. Pat. Nos. 3,720,617; 3,752,666; 3,788,994; 3,983,045; 4,051,077; 4,108,653; 4,258,116; and 4,558,108.
In addition, several patents illustrate toner resins including vinyl polymers, diolefins, and the like, reference for example U.S. Pat. No. 4,560,635. Moreover, there are illustrated in U.S. Pat. No. 4,469,770 toner and developer compositions wherein there are incorporated into the toner styrene butadiene resins prepared by emulsion polymerization process.
Furthermore, a number of different carrier particles have been illustrated in the prior art, reference for example U.S. Pat. No. 3,590,000 mentioned herein; and U.S. Pat. No. 4,233,387, the disclosures of which are totally incorporated herein by reference, wherein coated carrier components for developer mixtures, which are comprised of finely divided toner particles clinging to the surface of the carrier particles, are recited. Specifically, there are disclosed coated carrier particles obtained by mixing carrier core particles of an average diameter of from between about 30 microns to about 1,000 microns with from about 0.05 percent to about 3.0 percent by weight based on the weight of the coated carrier particles of thermoplastic resin particles. More specifically, there are illustrated in the '387 patent processes for the preparation of carrier particles by a powder coating process, and wherein the carrier particles consist of a core with a coating thereover comprised of polymers. The carrier particles selected can be prepared by mixing low density porous magnetic, or magnetically attractable metal core carrier particles with from, for example, between about 0.05 percent and about 3 percent by weight based on the weight of the coated carrier particles of a polymer until adherence thereof to the carrier core by mechanical impaction or electrostatic attraction; heating the mixture of carrier core particles and polymer to a temperature, for example, of between from about 200.degree. F. to about 550.degree. F. for a period of from about 10 minutes to about 60 minutes enabling the polymer to melt and fuse to the carrier core particles; cooling the coated carrier particles; and thereafter classifying the obtained carrier particles to a desired particle size. In U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference, there are illustrated, for example, carrier particles comprised of a core with a coating thereover comprised of a mixture of a first dry polymer component and a second dry polymer component not in close proximity to the first polymer in the triboelectric series. Therefore, the aforementioned carrier compositions can be comprised of known core materials including iron with a dry polymer coating mixture thereover. Subsequently, developer compositions can be generated by admixing the aforementioned carrier particles with a toner composition comprised of resin particles and pigment particles. Other patents include U.S. Pat. No. 3,939,086, which teaches steel carrier beads with polyethylene coatings, see column 6; U.S. Pat. No. 3,533,835; 3,658,500; 3,798,167, 3,918,968, 3,922,382; 4,238,558; 4,310,611; 4,397,935 and 4,434,220.
In copending application U.S. Ser. No. 751,922, now abandoned, entitled Developer Compositions With Specific Carrier Particle Developers, the disclosure of which is totally incorporated herein by reference there are illustrated toners with styrene butadiene copolymers, pigment particles inclusive of magnetites, charge controlled additives, and carrier particles containing a core with a coating thereover of vinyl copolymers, or homopolymers, such as vinyl chloride/vinyl acetate.
Semicrystaline polyolefin resins or blends thereof are illustrated in U.S. Pat. No. 4,490,424 and U.S. Pat. No. 4,952,477, the disclosures of which are totally incorporated herein by reference. More specifically, in U.S. Pat. No. 4,952,477 there are disclosed toners with semicrystalline polyolefin polymer or polymers with a melting point of from about 50 l to about 100.degree. C., and preferably from about 60.degree. to about 80.degree. C. with the following formulas wherein x is a number of from about 250 to about 21,000; the number average molecular weight is from about 17,500 to about 1,500,000 as determined by GPC; and the M.sub.w /M.sub.n dispersity ratio is from about 2 to about 15.
Examples of specific semicrystalline polyolefin polymers illustrated in this copending application include poly-1-pentene; poly-1-tetradecene; poly-1-pentadecene; poly-1-hexadecene; poly-1-heptadence; poly-1-octadene; poly-1-nonadecene; poly-1-eicosene; mixtures thereof; and the like.
Although the above described toner compositions and resins are suitable for their intended purposes, especially those of U.S. Pat. No. 4,952,477 and U.S. Pat. No. 4,490,424 in most instances, there continues to be a need for toner and developer compositions containing new resins. More specifically, there is a need for toners which can be fused at lower energies than many of the presently available resins selected for toners but which retain many or all of the same desirable physical properties, for example, hardness, processibility, durability, and the like. There is also a need for resins that can be selected for toner compositions which are low cost, nontoxic, nonblocking at temperatures of less than 50.degree. C., jettable, melt fusible with a broad fusing latitude, cohesive above the melting temperature, and triboelectrically chargeable. In addition, there remains a need for toner compositions, especially low melt toners, which can be fused at low temperatures, that is for example 260.degree. F. or less, as compared to a number presently in commercial use, which require fusing temperatures of about 300.degree. to 325.degree. F., thereby enabling with the compositions of the present invention the utilization of lower fusing temperatures, and lower fusing energies permitting less power consumption during fusing, and allowing the fuser system, particularly the fuser roll selected, to possess extended lifetimes. Another need resides in the provision of developer compositions comprised of the toner compositions illustrated herein, and carrier particles. There also remains a need for toner and developer compositions containing additives therein, for example charge enhancing components, thereby providing positively or negatively charged toner compositions. Furthermore, there is a need for toner and developer compositions with multiblock polymers that will enable the generation of solid image area with substantially no background deposits, and full gray scale production of half tone images in electrophotographic imaging and printing systems.
There is also a need for multiblock polymers and copolymers thereof, and mixtures of the aforementioned polymers and copolymers with glass transition temperatures of, for example, from about 20.degree. to about 70.degree. C., and preferably from about 33.degree. to about 60.degree. C.; and wherein toner compositions containing the aforementioned resins can be formulated into developer compositions which are useful in electrophotographic imaging and printing systems, and wherein fusing can, for example, be accomplished by flash, radiant, with heated ovens, cold pressure, and heated roller fixing methods, in embodiments of the present invention.